Black sulfur dye and process of making same.



Nirino firarns PATENT FFICE.

FRIEDRICH REUBOLD, OF LUDXVIGSHAFEN, GERMANY, ASSIGNOR TO BADISOI'IEANILIN AND SODA FABRIK, OF LUD\VIGSHAFEN, GER- MANY, A CORPORATION OFGERMANY.

BLACK SULFUR DYE AND PROCESS OF MAKING SAME.

.PEQEFEGATION forming part of Let ers Patent No, 695,835, dated March18, 1902.

Application filed December 23, 1901. Serial No. 87,012. (No specimens.)

To all whom it may concern.-

Be it known that I, FRIEDRICH REUBoLD, doctor of philosophy and chemist,and a subject of the King of Bavaria, residing atLudwigshafen-on-the-Rhine, in the Kingdom of Bavaria, Germany, haveinvented new and useful Improvements in Black Coloring-Matters, of whichthe following is a specification.

This invention relates to a new substantive black coloring-matter forcotton.

In this invention use is made of a product arising from the action oftrinitro-meta-dichlor-benzene on para-amido-phenol. This product whensuitably heated with sodium sulfid and sulfur yields the new blackcoloring-matter.

The nature of this invention is furtherillustrated in the followingexamples. The invention, however, is not limited to the conditions andproportions therein given. The parts are by weight, and the temperaturedegrees refer to the centigrade scale.

Emample 1-Pr0duczfion of trim'zro-meiadichlor benzenc.Introduce fourhundred (400) parts of dinitro-meta-dichlor-benzene into a mixture oftwo hundred and eighty (280) parts of nitric acid containing ninetyfour(94) per cent. of that acid (HNO and eight hundred (800) parts of fumingsulfuric acid containing twenty-three (23) per cent. of free sulfuricanhydride,(SO Heat the whole for about three hours to a temperature offrom one hundred and forty to one hundred and forty-five degrees,stirring the meanwhile. Cool and pour the result upon twenty-fivehundred (2500) parts of ice. O01- lect the solid material, and, ifdesired, it may be purified by recrystallization from alcohol. Sopurified this trinitro-para-dichlor-benzene melts at about one hundredand twenty-eight (128) degrees.

Example 2-Produc1fion of cZ ipara hydroxy p71 cng Z irinitro meta phony[cue climmm-Pour two thousand (2,000) parts of alcohol upon one hundredand forty (140) parts of trinitro-meta-dichlor-benzene, one hundred andfifty parts of the hydrochloric salt of para-amido-phenol, and threehundred (300) parts of crystallized sodium acetate. Heat to boilingunder a return-condenser, stirring the meanwhile. Continue this untilfurther increase in the quantity of the red product is not observable.

Now filter and wash the solid material with water and dry it. Thedipara-hydroxy-phenyl-trinitrometa-pheuylene-diamin so obtained can becrystallized from ethyl alcohol in the form of brick-red leaflets, whichmelt, with decomposition, at about two hundred and twenty-five (225)degrees.

Example 3Pr0duction of coloring-matter.lntroduce fifty (50) parts ofdipara-hyd roxyphenyl trinitro meta phenylene diamin into a mixture oftwo hundred (200) parts of crystallized sodium sulfid, sixty (60) partsof sulfur, and two hundred (200) parts of water. Stir the whole andgradually raise its temperature, which induces a vigorous reaction. Whenthis has subsided somewhat, gradually raise the temperature by means of,say, an oil-bath to about one hundred and sixty to one hundred andeighty (180) degrees and maintain this temperature until the melt hassolidified and can be reduced to powder. Cool and powder this result,which may be directly employed in dyeing.

The so-obtained product is of a black color and produces agreenish-colored solution with water, which solution becomes bluer byaddition of sodium sulfid to it. With concentrated sulfuric acid itproduces a dirty-green color. It dyes cotton a greenish-black shade,which is rendered of a bluer cast by treatment with a solution ofhydrogen peroxid to which ammonia has been added.

WVhat is claimed is As a new article of manufacture blackcoloring-matter which can be made from diparahydroXy-diphenyl-trinitrometa phenylenediamin, sulfur and sodium sulfid, which is a blacksubstance soluble in water giving a greenish-colored solution whichsolution becomes bluer on treatment with sodium sulfid, whichcoloring-matter gives a dirtygreen color with concentrated sulfuric acidand dyes unmordanted cotton a greenish-black shade which is rendered ofa bluer cast by treatment with a solution of hydrogen peroxid to whichsome ammonia has been added.

In testimony whereof I have hereunto set my hand in presence of twosubscribing wit- DGSSGS.

FRIEDRICH REUBOLD. \Vitnesses:

BERNHARD C. I-Inssn, JAoon ADRIAN.

